TW201301635A - Separator having heat resistant insulation layers - Google Patents

Separator having heat resistant insulation layers Download PDF

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TW201301635A
TW201301635A TW101122204A TW101122204A TW201301635A TW 201301635 A TW201301635 A TW 201301635A TW 101122204 A TW101122204 A TW 101122204A TW 101122204 A TW101122204 A TW 101122204A TW 201301635 A TW201301635 A TW 201301635A
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heat
insulating layer
resistant insulating
separator
layer
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TW101122204A
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TWI466365B (en
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Hironobu Muramatsu
Tamaki Hirai
Kazuki Miyatake
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Nissan Motor
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Abstract

A separator (1) having heat resistant insulation layers, for electric devices, according to the present invention is provided with: a resin porous substrate (2); and heat resistant insulation layers (3) that are formed on both faces of the resin porous substrate, and that comprise heat resistant particles the melting point or thermal softening point of which is not less than 150 DEG C. A parameter (X) indicated by numerical formula (1) has a value not less than 0.15. In this numerical formula, A' and A'' are thicknesses (μm) of each of the heat resistant insulation layers (3) formed on both faces of the resin porous substrate (2), have a relationship of A' ≥ A'' in this case, and C is the total thickness (μm) of the separator (1) having the heat resistant insulation layers. Numerical formula (1)

Description

附有耐熱絕緣層之隔離層 Isolation layer with heat resistant insulation

本發明係關於附有耐熱絕緣層之隔離層。 The present invention relates to an isolation layer with a heat resistant insulating layer.

近幾年來，為因應地球暖化，而熱切期望二氧化碳量之減低。因此，於汽車業界，聚焦於藉由電動汽車(EV)或油電混合汽車(HEV)之導入而期待二氧化碳排出量之減低。為此，已擴大進行掌握該等實用化關鍵之馬達驅動用蓄電池等之電裝置開發。 In recent years, in response to global warming, it is eagerly expected to reduce the amount of carbon dioxide. Therefore, in the automotive industry, the focus is on the reduction of carbon dioxide emissions by the introduction of electric vehicles (EV) or hybrid electric vehicles (HEV). For this reason, development of electric devices such as batteries for driving motors that are critical to such practical use has been expanded.

尤其，鋰離子蓄電池由於其能量密度高且對於反覆充放電之耐久性高故認為可較好地使用於電動車輛，且處於進一步朝高電容化進展之傾向。為此，鋰離子蓄電池之安全性確保益發重要。 In particular, lithium ion batteries are considered to be excellent for use in electric vehicles because of their high energy density and high durability against reverse charge and discharge, and tend to progress toward higher capacitance. For this reason, the safety of lithium-ion batteries ensures that it is important.

鋰離子蓄電池一般具備於正極集電體之兩面上塗佈正極活性物質之正極、於負極集電體之兩面上塗佈負極活性物質之負極。接著，透過於隔離層中保持電解液或電解質膠之電解質層，使前述正極及負極連接。隨後，將正極、負極及隔離層收納於電池盒中。 A lithium ion secondary battery generally includes a positive electrode coated with a positive electrode active material on both surfaces of a positive electrode current collector, and a negative electrode coated with a negative electrode active material on both surfaces of the negative electrode current collector. Next, the electrolyte and the electrolyte layer of the electrolyte paste are held in the separator to connect the positive electrode and the negative electrode. Subsequently, the positive electrode, the negative electrode, and the separator are housed in a battery case.

至於隔離層，大多使用例如厚度為20~30μm左右之聚乙烯微多孔膜。然而，該等聚乙烯微多孔膜，有因電池內之溫度上升導致熱收縮以及伴隨此而發生短路之可能性。 As the separator, a polyethylene microporous film having a thickness of, for example, about 20 to 30 μm is often used. However, these polyethylene microporous membranes are likely to cause heat shrinkage due to an increase in temperature in the battery and a short circuit accompanying this.

因此，為抑制隔離層之熱收縮，已開發於微多孔膜表 面上層合耐熱性多孔質層之附有耐熱絕緣層之隔離層。例如，於專利文獻1中，記載有將該種隔離層使用於捲取型鋰離子電池，而抑制因電池內溫度上升引起之熱收縮。 Therefore, in order to suppress the thermal shrinkage of the separator, it has been developed in the microporous membrane table. An insulating layer of a heat-resistant insulating layer is attached to the surface-heat-resistant porous layer. For example, Patent Document 1 describes that such a separator is used for a coil-type lithium ion battery, and heat shrinkage due to an increase in temperature inside the battery is suppressed.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]國際公開第2007/066768號 [Patent Document 1] International Publication No. 2007/066768

然而，專利文獻1中記載之隔離層若應用於平板層合型之非水電解質系蓄電池，則於電池製造時會於隔離層端部發生捲曲，而發生捲曲部分被折入並就此層合之問題。由其於如使用於電動汽車般之大型電池時，由於一構件面積較大，故即使僅稍許變形亦有於操作中產生缺陷之情況，而使良率大幅降低。 However, when the separator described in Patent Document 1 is applied to a non-aqueous electrolyte-based battery of a flat-plate laminate type, curling occurs at the end of the separator at the time of battery manufacture, and the curled portion is folded and laminated. problem. When it is used in a large-sized battery such as an electric car, since a large area of a member is large, even if it is only slightly deformed, a defect occurs in the operation, and the yield is greatly lowered.

本發明係鑑於此種先前技術所具有之課題而完成者。因此，其目的係提供可穩定地製造捲曲之發生受到抑制、信賴性高之電裝置之附有耐熱絕緣層之隔離層。 The present invention has been accomplished in view of the problems of such prior art. Therefore, it is an object of the invention to provide an insulating layer with a heat-resistant insulating layer which can stably produce an electric device having suppressed occurrence of curl and high reliability.

本發明樣態之附有耐熱絕緣層之隔離層具備樹脂多孔質基體及形成於樹脂多孔質基體兩面上之含有熔點或熱軟化點為150℃以上之耐熱粒子之耐熱絕緣層。而且，特徵為以數式1表示之參數X為0.15以上。 The separator having the heat-resistant insulating layer in the aspect of the invention includes a resin porous substrate and a heat-resistant insulating layer formed on both surfaces of the resin porous substrate and containing heat-resistant particles having a melting point or a thermal softening point of 150 ° C or higher. Further, the parameter X represented by the formula 1 is 0.15 or more.

式中，A’及A”為形成於樹脂多孔質基體兩面上之各耐熱絕緣層之厚度(μm)，此時，A’≧A”，C為附有耐熱絕緣層之隔離層之總厚度(μm)。 Wherein A' and A" are the thickness ( μm ) of each of the heat-resistant insulating layers formed on both sides of the porous resin substrate, and at this time, A'≧A", C is the total of the separators with the heat-resistant insulating layer. Thickness ( μ m).

以下，邊參考圖式邊針對本發明之電裝置用之附有耐熱絕緣層之隔離層及電裝置加以說明。又，圖式說明中相同要件附以相同符號，並省略重覆說明。且，圖式之尺寸比例為方便說明而有誇張，有與實際比例不同之情況。 Hereinafter, the separator and the electric device with the heat-resistant insulating layer for the electric device of the present invention will be described with reference to the drawings. In the drawings, the same elements are denoted by the same reference numerals, and the repeated description is omitted. Moreover, the size ratio of the drawings is exaggerated for convenience of explanation, and there are cases where the actual ratio is different.

本發明之一實施形態之電裝置用之附有耐熱絕緣層之隔離層以及使用其之電裝置，即使為大型平板層合型電裝置於各要件層合時亦難以產生缺陷，而提高生產性。為此，使用本實施形態之附有耐熱絕緣層之隔離層的電裝置，尤其是非水電解質系蓄電池使用作為車輛之驅動電源用或輔助電源用較為優異。 The insulating layer with a heat-resistant insulating layer for an electric device according to an embodiment of the present invention, and an electric device using the same, are difficult to produce defects even when a large-sized flat laminated electric device is laminated on each element, thereby improving productivity. . For this reason, the electric device using the separator having the heat-resistant insulating layer of the present embodiment, in particular, the non-aqueous electrolyte-based battery is preferably used as a driving power source for an automobile or an auxiliary power source.

亦即，本實施形態之電裝置只要是使用下述說明之附有耐熱絕緣層之隔離層者即可，關於其他構成要件，則無特別限制。又，本實施形態中，作為電裝置係例示為鋰離子蓄電池加以說明。 In other words, the electric device of the present embodiment is not particularly limited as long as it is a separator having a heat-resistant insulating layer as described below. Further, in the present embodiment, an electric device is exemplified as a lithium ion battery.

例如，作為鋰離子電池之使用形態，可使用鋰離子原電池(一次電池)及鋰離子蓄電池(二次電池)之任一種。較好由於高循環耐久性亦優異，故而期望作為鋰離子蓄電池而利用於車輛之驅動電源用等或行動電話等之攜帶機器等。 For example, as a form of use of the lithium ion battery, any of a lithium ion primary battery (primary battery) and a lithium ion secondary battery (secondary battery) can be used. In addition, since it is excellent in high cycle durability, it is desired to be used as a lithium ion battery for a driving device such as a driving power source of a vehicle or a mobile phone.

上述附有耐熱絕緣層之隔離層可應用於平板層合型(扁平型)電池。藉由採用平板層合型之電池構造，可利用簡單之熱壓著等之密封技術而確保長期信賴性，就成本面及作業性方面為有利。 The above-mentioned separator having a heat resistant insulating layer can be applied to a flat laminated type (flat type) battery. By adopting the flat laminated type battery structure, it is possible to secure long-term reliability by using a sealing technique such as simple heat pressing, which is advantageous in terms of cost and workability.

又，以鋰離子蓄電池內之電連接形態(電極構造)來看時，可應用於非雙極型電池(內部並聯連接類型)及雙極型電池(內部串聯連接類型)之任一種。 Further, when viewed in the form of an electrical connection (electrode structure) in a lithium ion secondary battery, it can be applied to any of a non-bipolar battery (internal parallel connection type) and a bipolar battery (internal series connection type).

再者，上述附有耐熱絕緣層之隔離層可應用於使用非水系之電解液等之溶液電解質之溶液電解質型電池。再者。亦可應用於使用高分子膠電解質之膠體電解質型電池等之電解質層中。 Further, the above-mentioned separator having the heat resistant insulating layer can be applied to a solution electrolyte type battery using a solution electrolyte such as a nonaqueous electrolyte. Again. It can also be applied to an electrolyte layer such as a colloidal electrolyte type battery using a polymer gel electrolyte.

因此，以下說明，係使用圖式，說明使用本實施形態之附有耐熱絕緣層之隔離層的非雙極型鋰離子蓄電池。 Therefore, in the following description, a non-bipolar lithium ion secondary battery using the insulating layer with a heat resistant insulating layer of the present embodiment will be described using a drawing.

[電池之全體構造] [The whole structure of the battery]

圖1係顯示本發明一實施形態之平板層合型(扁平型)之鋰離子蓄電池全體構造。又，平板層合型之鋰離子蓄電池亦簡稱為「層合型電池」。 Fig. 1 is a view showing the entire structure of a flat-plate laminated (flat type) lithium ion secondary battery according to an embodiment of the present invention. Further, the flat-plate type lithium ion battery is also simply referred to as a "laminated battery".

如圖1所示，本實施形態之層合型電池10具有進行充放電反應之略矩形發電要件21被封裝於電池外裝材29內部之構造。此處，發電要件21具有將正極、電解質層17及負極層合之構成。正極係於正極集電體11之兩面上配置正極活性物質層13而構成。又，電解質層17係於隔離層中保持電解質(電解液或電解質膠)之構成。再者， 負極係於負極集電體12之兩面上配置負極活性物質層15而構成。若換言之，則以將一個正極活性物質層13及與其鄰接之負極活性物質層15介隔電解質層17予以對向之方式，依序層合負極、電解質層及正極。 As shown in FIG. 1, the laminated battery 10 of the present embodiment has a structure in which a rectangular power generation element 21 that performs a charge and discharge reaction is sealed inside the battery exterior material 29. Here, the power generation element 21 has a configuration in which a positive electrode, an electrolyte layer 17, and a negative electrode are laminated. The positive electrode is configured by disposing the positive electrode active material layer 13 on both surfaces of the positive electrode current collector 11 . Further, the electrolyte layer 17 is configured to hold an electrolyte (electrolyte or electrolyte gel) in the separator. Furthermore, The negative electrode is configured by disposing the negative electrode active material layer 15 on both surfaces of the negative electrode current collector 12 . In other words, the negative electrode, the electrolyte layer, and the positive electrode are sequentially laminated in such a manner that one positive electrode active material layer 13 and the negative electrode active material layer 15 adjacent thereto are opposed to each other via the electrolyte layer 17.

藉此，鄰接之正極、電解質層及負極構成一個單電池層19。圖1所示之層合型電池10亦可說具有藉由將單電池層19複數層合且電性上並聯連接之構成。又，位於發電要件21之兩最外層之正極集電體上，分別僅於單面配置正極活性物質層13，但亦可於兩面上設有正極活性物質層。亦即，亦可不成為於僅單面設有正極活性物質層之最外層專用集電體，而將於兩面上有正極活性物質層之集電體直接作為最外層之集電體使用。又，亦可藉由將圖1中正極及負極之配置相反，而將負極集電體位於發電要件21之兩最外層之方式，僅於最外層之負極集電體之單面或雙面上配置負極活性物質層。 Thereby, the adjacent positive electrode, electrolyte layer and negative electrode constitute one single cell layer 19. The laminated battery 10 shown in Fig. 1 can also be constructed by laminating a plurality of battery cells 19 and electrically connecting them in parallel. Moreover, the positive electrode active material layer 13 is disposed only on one surface of the positive electrode current collectors of the two outermost layers of the power generation element 21, but the positive electrode active material layer may be provided on both surfaces. In other words, the current collector of the outermost layer in which the positive electrode active material layer is provided on only one side is not used, and the current collector having the positive electrode active material layer on both surfaces is directly used as the collector of the outermost layer. Further, by arranging the positive electrode and the negative electrode in FIG. 1 oppositely, the negative electrode current collector can be positioned on the outermost layers of the power generating element 21, only on one or both sides of the outermost layer of the negative electrode current collector. The anode active material layer is disposed.

於正極集電體11及負極集電體12上，分別安裝有與各電極(正極及負極)導通之正極集電板25及負極集電板27。而且，正極集電板25及負極集電板27以夾持於電池外裝材29之端部之方式導出至電池外裝材29之外部。正極集電板25及負極集電板27亦可分別依據需要，介隔正極引線及負極引線(未圖示)，藉由超音波熔接或電阻熔接等而安裝於各電極之正極集電體11及負極集電體12上。 A positive electrode current collector 25 and a negative electrode current collector 27 that are electrically connected to the respective electrodes (positive electrode and negative electrode) are attached to the positive electrode current collector 11 and the negative electrode current collector 12, respectively. Further, the positive electrode current collecting plate 25 and the negative electrode current collecting plate 27 are led out to the outside of the battery exterior material 29 so as to be sandwiched between the end portions of the battery exterior material 29. The positive electrode current collector plate 25 and the negative electrode current collector plate 27 may be attached to the positive electrode current collector 11 of each electrode by ultrasonic welding or electric resistance welding, if necessary, via a positive electrode lead and a negative electrode lead (not shown). And the negative electrode current collector 12.

於上述說明之鋰離子蓄電池於隔離層中具有特徵。以 下，針對含有該隔離層之電池主要構成構件加以說明。 The lithium ion battery described above has characteristics in the separator. Take Next, the main constituent members of the battery including the separator will be described.

[活性物質層] [active material layer]

正極活性物質層13及負極活性物質層15含有活性物質且依據需要進而含有其他添加劑。 The positive electrode active material layer 13 and the negative electrode active material layer 15 contain an active material and further contain other additives as needed.

正極活性物質層13含有正極活性物質。至於正極活性物質舉例有例如LiMn2O4、LiCoO2、LiNiO2、Li(Ni-Co-Mn)O2及該等過渡金屬之一部分由其他元素取代者等之鋰-過渡金屬複合氧化物；鋰-過渡金屬磷酸化合物；鋰-過渡金屬流酸化合物等。依情況而定，亦可併用兩種以上之正極活性物質。由電容及輸出特性之觀點而言，較好使用鋰-過渡金屬複合氧化物作為正極活性物質。又，亦可使用上述以外之正極活性物質。 The positive electrode active material layer 13 contains a positive electrode active material. The positive electrode active material is exemplified by, for example, LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , Li(Ni—Co—Mn)O 2 , and a lithium-transition metal composite oxide in which one of the transition metals is partially replaced by another element; A lithium-transition metal phosphate compound; a lithium-transition metal acid compound or the like. Two or more kinds of positive electrode active materials may be used in combination depending on the circumstances. From the viewpoint of capacitance and output characteristics, a lithium-transition metal composite oxide is preferably used as the positive electrode active material. Further, a positive electrode active material other than the above may be used.

負極活性物質層15含有負極活性物質。至於負極活性物質，舉例有例如石墨(graphite)、軟碳及硬碳等之碳材料；鋰-過渡金屬複合氧化物(例如Li4Ti5O12)；金屬材料；鋰合金系負極材料等。依情況而定，亦可併用兩種以上之負極活性物質。由電容及輸出特性之觀點而言，較好使用碳材料或鋰-過渡金屬複合氧化物作為負極活性物質。又，亦可使用上述以外之負極活性物質。 The negative electrode active material layer 15 contains a negative electrode active material. Examples of the negative electrode active material include carbon materials such as graphite, soft carbon, and hard carbon; lithium-transition metal composite oxides (for example, Li 4 Ti 5 O 12 ); metal materials; and lithium alloy negative electrode materials. Two or more kinds of negative electrode active materials may be used in combination depending on the case. From the viewpoint of capacitance and output characteristics, a carbon material or a lithium-transition metal composite oxide is preferably used as the negative electrode active material. Further, a negative electrode active material other than the above may also be used.

正極活性物質層13及負極活性物質層15中所含之各活性物質之平均粒徑並未特別限制，但基於高輸出化之觀點，較好為1~100μm，更好為1~20μm。 The average particle diameter of each active material contained in the positive electrode active material layer 13 and the negative electrode active material layer 15 is not particularly limited, but is preferably from 1 to 100 μm , more preferably from 1 to 20, from the viewpoint of high output. μ m.

又，正極活性物質層13及負極活性物質層15較好含 有黏合劑。正極活性物質層13及負極活性物質層15中所用之黏合劑並未特別限定。作為黏合劑，舉例有例如聚乙烯、聚丙烯、聚對苯二甲酸乙二酯(PET)、聚醚腈、聚丙烯腈、聚醯亞胺、聚醯胺、纖維素、羧甲基纖維素(CMC)、乙烯-乙酸乙烯酯共聚物、聚氯乙烯、苯乙烯-丁二烯橡膠(SBR)、異戊二烯橡膠、丁二烯橡膠、乙烯．丙烯橡膠、乙烯．丙烯．二烯共聚物、苯乙烯．丁二烯．苯乙烯嵌段共聚物及其氫化物、苯乙烯．異戊二烯．苯乙烯嵌段共聚物及其氫化物等之熱可塑性高分子。又，作為黏合劑，舉例有聚偏氟化乙烯(PVdF)、聚四氟乙烯(PTFE)、四氟乙烯．六氟丙烯共聚物(FEP)、四氟乙烯．全氟烷基乙烯醚共聚物(PFA)、乙烯．四氟乙烯共聚物(ETFE)、聚氯三氟乙烯(PCTFE)、乙烯．氯三氟乙烯共聚物(ECTFE)、聚氟化乙烯(PVF)等氟樹脂。再者，作為黏合劑，亦舉例有偏氟乙烯-六氟丙烯系氟橡膠(VDF-HFP系氟橡膠)、偏氟乙烯-六氟丙烯-四氟乙烯系氟橡膠(VDF-HFP-TFE系氟橡膠)、偏氟乙烯-五氟丙烯系氟橡膠(VDF-PFP系氟橡膠)、偏氟乙烯-五氟丙烯-四氟乙烯系氟橡膠(VDF-PFP-TFE系氟橡膠)、偏氟乙烯-全氟甲基乙烯醚-四氟乙烯系氟橡膠(VDF-PFMVE-TFE系氟橡膠)、偏氟乙烯-氯三氟乙烯系氟橡膠(VDF-CTFE系氟橡膠)等之偏氟乙烯系氟橡膠。又，作為黏合劑，亦舉例有環氧樹脂等。其中更好為聚偏氟乙烯、聚醯亞胺、苯乙烯．丁二烯橡膠、羧甲基纖維素、聚丙烯、聚四氟乙烯 、聚丙烯腈、聚醯胺。該等黏合劑，由於耐熱性優異，進而電位範圍非常廣，於正極電位及負極電位均為安定，故可較好地使用於活性物質層。該等黏合劑可單獨使用亦可組合兩種以上使用。 Further, the positive electrode active material layer 13 and the negative electrode active material layer 15 preferably contain There are adhesives. The binder used in the positive electrode active material layer 13 and the negative electrode active material layer 15 is not particularly limited. As the binder, for example, polyethylene, polypropylene, polyethylene terephthalate (PET), polyether nitrile, polyacrylonitrile, polyimide, polyamine, cellulose, carboxymethyl cellulose are exemplified. (CMC), ethylene-vinyl acetate copolymer, polyvinyl chloride, styrene-butadiene rubber (SBR), isoprene rubber, butadiene rubber, ethylene. Acrylic rubber, ethylene. Propylene. Diene copolymer, styrene. Butadiene. Styrene block copolymer and its hydride, styrene. Isoprene. A thermoplastic polymer such as a styrene block copolymer or a hydride thereof. Further, as the binder, polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), and tetrafluoroethylene are exemplified. Hexafluoropropylene copolymer (FEP), tetrafluoroethylene. Perfluoroalkyl vinyl ether copolymer (PFA), ethylene. Tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene. A fluororesin such as chlorotrifluoroethylene copolymer (ECTFE) or polyvinyl fluoride (PVF). Further, examples of the binder include a vinylidene fluoride-hexafluoropropylene-based fluororubber (VDF-HFP fluororubber) and a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene fluororubber (VDF-HFP-TFE system). Fluororubber), vinylidene fluoride-pentafluoropropylene fluororubber (VDF-PFP fluororubber), vinylidene fluoride-pentafluoropropylene-tetrafluoroethylene fluororubber (VDF-PFP-TFE fluororubber), defluorinated Vinylidene-perfluoromethylvinyl ether-tetrafluoroethylene fluororubber (VDF-PFMVE-TFE fluororubber), vinylidene fluoride-chlorotrifluoroethylene fluororubber (VDF-CTFE fluororubber) Fluororubber rubber. Further, as the binder, an epoxy resin or the like is also exemplified. Among them, polyvinylidene fluoride, polyimine, and styrene are preferred. Butadiene rubber, carboxymethyl cellulose, polypropylene, polytetrafluoroethylene , polyacrylonitrile, polyamine. These binders are excellent in heat resistance and have a wide potential range, and are stable in both the positive electrode potential and the negative electrode potential, so that they can be preferably used in the active material layer. These binders may be used singly or in combination of two or more.

活性物質層中所含之黏合劑量，只要為可使活性物質黏結之量即無特別限定。然而，黏合劑量較好對於活性物質層為0.5~15質量%，更好為1~10質量%。 The amount of the binder contained in the active material layer is not particularly limited as long as it can bind the active material. However, the bonding amount is preferably from 0.5 to 15% by mass, more preferably from 1 to 10% by mass, based on the active material layer.

至於活性物質層中所含之其他添加劑，舉例有例如導電助劑、電解質鹽、離子傳導性聚合物等。 As the other additives contained in the active material layer, for example, a conductive auxiliary agent, an electrolyte salt, an ion conductive polymer, or the like can be exemplified.

所謂導電助劑，指用以提高正極活性物質層或負極活性物質層之導電性而調配之添加物。作為導電助劑，舉例有乙炔黑等之碳黑、石墨、碳纖維等之碳材料。活性物質層若包含導電助劑，則可有效地形成活性物質層內部之電子網路，有助於電池輸出特性之提高。 The conductive auxiliary agent refers to an additive which is prepared to increase the conductivity of the positive electrode active material layer or the negative electrode active material layer. Examples of the conductive auxiliary agent include carbon materials such as carbon black such as acetylene black, graphite, and carbon fibers. When the active material layer contains a conductive auxiliary agent, the electronic network inside the active material layer can be effectively formed, which contributes to an improvement in battery output characteristics.

至於電解質鹽(鋰鹽)舉例有Li(C2F5SO2)2N、LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3等。 Examples of the electrolyte salt (lithium salt) include Li(C 2 F 5 SO 2 ) 2 N, LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 and the like.

作為離子傳導性聚合物，舉例有例如聚氧化乙烯(PEO)系及聚氧化丙烯(PPO)系之聚合物。 Examples of the ion conductive polymer include a polyethylene oxide (PEO) system and a polyoxypropylene (PPO) polymer.

正極活性物質層及負極活性物質層中所含成分之調配比並無特別限定。調配比可藉由適當參考非水電解質系蓄電池中之公知見解而調整。各活性物質層之厚度亦未特別限制，可適當參考關於電池之以往公知見解。若舉一例，則各活性物質層之厚度為2~100μm左右。 The compounding ratio of the components contained in the positive electrode active material layer and the negative electrode active material layer is not particularly limited. The compounding ratio can be adjusted by appropriately referring to well-known knowledge in the nonaqueous electrolyte battery. The thickness of each active material layer is also not particularly limited, and a conventionally known knowledge regarding a battery can be appropriately referred to. As an example, the thickness of each active material layer is about 2 to 100 μm .

[集電體] [Collector]

正極集電體11及負極集電體12係由導電性材料構成。集電體大小係對應於電池使用用途而決定。例如於要求高能量密度之大型電池之情況，則使用面積較大之集電體。本實施形態之鋰離子電池較好為大型電池，所用集電體大小為例如長邊為100mm以上，較好為100mm×100mm以上，更好為200mm×200mm以上。集電體厚度亦無特別限制。集電體厚度通常為1~100μm左右。關於集電體之形狀亦未特別限制。圖1所示之層合型電池10中，除集電箔以外，可使用網眼形狀(擴張柵板等)。 The positive electrode current collector 11 and the negative electrode current collector 12 are made of a conductive material. The size of the collector is determined according to the use of the battery. For example, in the case of a large battery requiring a high energy density, a current collector having a large area is used. The lithium ion battery of the present embodiment is preferably a large-sized battery, and the size of the current collector used is, for example, a long side of 100 mm or more, preferably 100 mm × 100 mm or more, more preferably 200 mm × 200 mm or more. The thickness of the current collector is also not particularly limited. The collector thickness is usually about 1 to 100 μm . The shape of the current collector is also not particularly limited. In the laminated battery 10 shown in Fig. 1, a mesh shape (expanded grid or the like) can be used in addition to the current collector foil.

構成集電體之材料並未特別限制，較好採用金屬。具體舉例為鋁、鎳、鐵、不鏽鋼、鈦、銅等。除該等以外，可較好地使用鎳與鋁之包覆材、銅與鋁之包覆材、或該等金屬之組合的鍍敷材等。又，亦可為於金屬表面被覆鋁之箔。其中，由電子傳導性或電池作動電位之觀點，較好為鋁、不鏽鋼及銅。 The material constituting the current collector is not particularly limited, and a metal is preferably used. Specific examples are aluminum, nickel, iron, stainless steel, titanium, copper, and the like. In addition to these, a clad material of nickel and aluminum, a clad material of copper and aluminum, or a plating material of a combination of these metals can be preferably used. Further, it may be a foil coated with aluminum on a metal surface. Among them, aluminum, stainless steel, and copper are preferred from the viewpoint of electron conductivity or battery actuation potential.

[電解質層] [electrolyte layer]

電解質層17具有於本實施形態之隔離層之面方向中央保持有電解質之構成。藉由使用本實施形態之隔離層，可抑制層合時端部捲曲發生，故可穩定地製造信賴性高的電池。 The electrolyte layer 17 has a structure in which an electrolyte is held at the center in the surface direction of the separator in the present embodiment. By using the separator of the present embodiment, occurrence of curling of the end portion during lamination can be suppressed, so that a highly reliable battery can be stably produced.

(附有耐熱絕緣層之隔離層) (with insulation layer of heat-resistant insulation layer)

本實施形態之附有耐熱絕緣層之隔離層具備樹脂多孔質基體及形成於樹脂多孔質基體兩面上之含有熔點或熱軟化點為150℃以上之耐熱粒子之耐熱絕緣層。而且，前述隔離層之特徵為以下述數式(1)表示之參數X為0.15以上。 The separator having the heat-resistant insulating layer of the present embodiment includes a resin porous substrate and a heat-resistant insulating layer formed on both surfaces of the resin porous substrate and containing heat-resistant particles having a melting point or a thermal softening point of 150 ° C or higher. Further, the separator is characterized in that the parameter X represented by the following formula (1) is 0.15 or more.

式中，A’及A”為形成於前述樹脂多孔質基體兩面上之各耐熱絕緣層(3)之厚度(μm)，此時，A’≧A”。而且，C為前述附有耐熱絕緣層之隔離層(1)之總厚度(μm)。 In the formula, A' and A" are the thickness ( μm ) of each heat-resistant insulating layer (3) formed on both surfaces of the resin porous substrate, and in this case, A'≧A". Further, C is the total thickness ( μm ) of the foregoing insulating layer (1) with a heat-resistant insulating layer.

依據本實施形態之隔離層，可抑制端部翹曲、捲曲之發生。因此，若使用本實施形態之隔離層，則可於平板層合型電池之製造步驟中，提高良率。上述參數X之值低於0.15時，捲曲變得無法忽視，尤其是製造大型平板層合型電池時，良率顯著降低。 According to the separator of the present embodiment, occurrence of warpage and curling of the end portion can be suppressed. Therefore, when the separator of the present embodiment is used, the yield can be improved in the manufacturing process of the flat laminate battery. When the value of the above parameter X is less than 0.15, the curl becomes inconsequential, and particularly when a large flat laminated battery is manufactured, the yield is remarkably lowered.

上述專利文獻1中記載之隔離層於應用於捲取型電池時，容易發生因隔離層產生捲曲引起之層合時之缺陷。然而，於應用於電動汽車用之鋰離子蓄電池等之大型平板層合型電池時，由於一構件之面積較大，故即使僅稍許變形亦有於操作中產生缺陷之情況。例如如圖2(a)所示，製作大型平板層合型電池時，一般係使用層合帶依序搬送負極5、隔離層1及正極4，以高速層合。然而，由於隔離層為較柔軟之構件，故搬送時若如圖2(b)所示於隔離層 上有捲曲部分時，會以捲入至層合體中之狀態層合。而且，會踩住捲入部分，捲曲之捲入部分會被折入而層合。如此情況下，由於會使電池短路，故良率大幅降低，會使成本提高。 When the separator described in Patent Document 1 is applied to a coil-type battery, defects in lamination due to curling of the separator are likely to occur. However, when it is applied to a large flat laminated battery such as a lithium ion battery for an electric vehicle, since the area of one member is large, even if it is only slightly deformed, there is a case where a defect occurs during operation. For example, as shown in FIG. 2(a), when a large-sized flat laminated battery is produced, the negative electrode 5, the separator 1 and the positive electrode 4 are generally conveyed by a laminating tape in order, and laminated at a high speed. However, since the isolation layer is a relatively soft member, it is placed in the isolation layer as shown in Fig. 2(b) during transportation. When there is a curled portion, it is laminated in a state of being wound into the laminate. Moreover, the entangled portion is stepped on, and the curled-in portion is folded and laminated. In this case, since the battery is short-circuited, the yield is greatly lowered, and the cost is increased.

此處，本實施形態之附有耐熱絕緣層之隔離層1，如圖3所示，具有於樹脂多孔質基體2之兩面上設置耐熱絕緣層3之構造。 Here, as shown in FIG. 3, the separator 1 having the heat-resistant insulating layer of the present embodiment has a structure in which the heat-resistant insulating layer 3 is provided on both surfaces of the resin porous substrate 2.

此處，隔離層捲曲之原因，認為係在樹脂多孔質基體上塗佈耐熱絕緣層，以溫風乾燥等加熱乾燥之際，會殘存熱應力之故。具體而言，樹脂多孔質基體中所含之樹脂由於加熱時之線膨脹係數較大，故樹脂多孔質基體經加熱乾燥後成為伸展狀態。另一方面，由於耐熱絕緣層係使用熔點或熱軟化點為150℃以上之耐熱粒子而形成，故於加熱乾燥之溫度範圍內線膨脹係數十分小，幾乎不膨脹。因此，塗佈後之加熱乾燥結束而回到室溫時，樹脂多孔質基體雖較大收縮，但耐熱絕緣層幾乎不收縮。其結果，樹脂多孔質基體與耐熱絕緣層產生收縮率差，樹脂多孔質基體欲收縮，而耐熱絕緣層抗其收縮之結果，樹脂多孔質基體以朝內側捲起形態發生捲曲。 Here, the reason why the separator is curled is that a heat-resistant insulating layer is applied to the porous resin substrate, and thermal stress remains when heated and dried by warm air drying or the like. Specifically, since the resin contained in the resin porous substrate has a large coefficient of linear expansion upon heating, the resin porous substrate is dried by heating and then stretched. On the other hand, since the heat-resistant insulating layer is formed using heat-resistant particles having a melting point or a thermal softening point of 150 ° C or higher, the linear expansion coefficient is extremely small in the temperature range of heating and drying, and hardly expands. Therefore, when the heating and drying after coating is completed and returned to room temperature, the resin porous substrate shrinks largely, but the heat-resistant insulating layer hardly shrinks. As a result, the resin porous substrate and the heat-resistant insulating layer are inferior in shrinkage ratio, and the resin porous substrate is intended to shrink, and as a result of the shrinkage resistance of the heat-resistant insulating layer, the resin porous substrate is curled in a rolled-up manner toward the inside.

此處本實施形態中，於樹脂多孔質基體2之兩面上塗佈耐熱絕緣層3，儘可能使耐熱絕緣層3之厚度A’、A”相同。藉此，於樹脂多孔質基體2之上下方向之耐熱絕緣層3之收縮應力之平衡獲得改善，可抑制捲曲。再者，將耐熱絕緣層3之厚度A’、A”相對於隔離層總厚度C控制在 特定關係。藉此，樹脂多孔質基體2之內部應力與耐熱絕緣層3之收縮應力之平衡獲得改善，可充分抑制捲曲。而且，使上述數式(1)之參數X在0.15以上。藉此，難以發生較大捲曲，可解決在層合操作中捲曲被折入而層合之問題。 In the present embodiment, the heat-resistant insulating layer 3 is applied to both surfaces of the resin porous substrate 2, and the thicknesses A' and A" of the heat-resistant insulating layer 3 are made the same as possible. Thereby, the resin porous substrate 2 is placed under the resin porous substrate 2. The balance of the shrinkage stress of the heat-resistant insulating layer 3 in the direction is improved, and the curl can be suppressed. Further, the thickness A', A" of the heat-resistant insulating layer 3 is controlled with respect to the total thickness C of the separator. Specific relationship. Thereby, the balance between the internal stress of the resin porous substrate 2 and the shrinkage stress of the heat resistant insulating layer 3 is improved, and the curl can be sufficiently suppressed. Further, the parameter X of the above formula (1) is made 0.15 or more. Thereby, it is difficult to cause a large curl, and the problem that the curl is folded in and laminated in the laminating operation can be solved.

以上述數式(1)表示之參數X為使在樹脂多孔質基體之兩面上形成之耐熱絕緣層因乾燥引起之收縮應力差是否顯然存在之指標，X值越小，意指耐熱絕緣層之收縮應力差顯然存在。對於樹脂多孔質基體之內部應力，兩面耐熱絕緣層中收縮應力差的影響較大時，容易發生捲曲。例如，耐熱絕緣層厚度A’、A”相比於隔離層總厚度C越小，則參數X之值變小。又，基於兩面之耐熱絕緣層之單位面積重差較大等理由，兩面之耐熱絕緣層厚度差較大時，X之值變小。本實施形態中隔離層中，上述參數X之值為0.15以上，較好為0.20以上。X之值低於0.15時，捲曲之影響變得無法忽視，於製造大型平板層合型電池時，良率顯著降低。又，此時之所謂「單位面積重」意指樹脂多孔質基體之每單位面積中之耐熱絕緣層重量(g/m2)。 The parameter X represented by the above formula (1) is an index for whether or not the shrinkage stress difference due to drying of the heat-resistant insulating layer formed on both surfaces of the resin porous substrate is apparent. The smaller the X value, the heat-resistant insulating layer The shrinkage stress difference clearly exists. When the internal stress of the resin porous substrate is large, and the influence of the difference in shrinkage stress in the heat-resistant insulating layer on both sides is large, curling is likely to occur. For example, the smaller the thickness A', A" of the heat-resistant insulating layer is smaller than the total thickness C of the insulating layer, the smaller the value of the parameter X is. Further, based on the difference in the weight per unit area of the heat-resistant insulating layer on both sides, the two sides are When the difference in thickness of the heat-resistant insulating layer is large, the value of X becomes small. In the separator of the present embodiment, the value of the parameter X is 0.15 or more, preferably 0.20 or more. When the value of X is less than 0.15, the influence of curl is changed. It cannot be ignored that the yield is remarkably lowered when manufacturing a large flat laminated battery. In addition, the term "weight per unit area" at this time means the weight of the heat resistant insulating layer per unit area of the resin porous substrate (g/m). 2 ).

又，以上述數式(1)表示之參數X之上限，只要可抑制隔離層之捲曲則無特別限定，但例如可為1.0。 Further, the upper limit of the parameter X expressed by the above formula (1) is not particularly limited as long as the curl of the separator can be suppressed, but may be, for example, 1.0.

再者，本實施形態之隔離層中，較好以下述數式(2)表示之參數Y為0.3~0.7之範圍。 Further, in the separator of the present embodiment, the parameter Y represented by the following formula (2) is preferably in the range of 0.3 to 0.7.

式中，X如上述定義，D為耐熱絕緣層3之孔隙率(%)。 In the formula, X is as defined above, and D is the porosity (%) of the heat resistant insulating layer 3.

如上述，本實施形態之隔離層中，以上述數式(1)表示之參數X之值越大，端部越容易產生捲曲。然而，若將耐熱絕緣層之厚度(A’、A”)增厚，則雖X之值變大，但離子透過性降低，會使速率特性降低。本發明人等，對抑制捲曲發生同時保有高速率特性之條件進行檢討之結果，發現除了耐熱絕緣層之厚度以外，耐熱絕緣層之孔隙率(數式(2)中之D)亦為支配速率特性之因素之一。亦即，為了抑制捲曲發生，獲得高速率特性，重要的是兩層之耐熱絕緣層藉由來自樹脂多孔質基體之兩面之適當擠壓力，均等地擠壓兩面。擠壓力太弱而有偏傾時容易產生捲曲，擠壓力太強時，有離子透過性降低，電池塑率特性降低之可能性。 As described above, in the separator of the present embodiment, the larger the value of the parameter X expressed by the above formula (1), the more easily the end portion is curled. However, when the thickness (A', A") of the heat-resistant insulating layer is increased, the value of X is increased, but the ion permeability is lowered, and the rate characteristic is lowered. The present inventors have suppressed the occurrence of curl while maintaining As a result of reviewing the conditions of the high-rate characteristics, it was found that in addition to the thickness of the heat-resistant insulating layer, the porosity of the heat-resistant insulating layer (D in the formula (2)) is also one of the factors governing the rate characteristics. Curl occurs and high rate characteristics are obtained. It is important that the two layers of heat-resistant insulating layer uniformly press both sides by appropriate pressing force from both sides of the resin porous substrate. The pressing force is too weak and tends to be generated when biased. When the crimping force is too strong, there is a possibility that the ion permeability is lowered and the battery rate characteristic is lowered.

以上述數式(2)表示之參數Y為兩層之耐熱絕緣層對樹脂多孔質基體之兩面擠壓力有多強、是否均等擠壓之指標。例如基於兩面之耐熱絕緣層之單位面積重之差過大等理由，於樹脂多孔質基體之兩面之擠壓力有偏傾時，Y值變小。又，因耐熱絕緣層較薄或孔隙率較大而使耐熱絕緣層之擠壓力較弱時Y之值亦變小。再者，隔離層總厚度C越大，Y之值越小。另一方面，因耐熱絕緣層較厚或孔 隙率較大而使耐熱絕緣層之擠壓力較強時Y之值亦變大。本實施形態之隔離層中，上述參數Y之值較好為0.3~0.7，更好為0.35~0.65。Y之值若為0.3以上，則難以發生捲曲。Y之值若為0.7以下，則可獲得高速率特性。 The parameter Y represented by the above formula (2) is an index of how strong the two-layer heat-resistant insulating layer is on the both sides of the resin porous substrate and whether it is uniformly extruded. For example, when the pressing force on both surfaces of the resin porous substrate is biased based on the difference in weight per unit area between the heat-resistant insulating layers on both sides, the Y value becomes small. Further, since the heat-resistant insulating layer is thin or the porosity is large, the value of Y is also small when the pressing force of the heat-resistant insulating layer is weak. Furthermore, the larger the total thickness C of the isolation layer, the smaller the value of Y. On the other hand, because the heat resistant insulation layer is thick or hole When the gap ratio is large and the pressing force of the heat-resistant insulating layer is strong, the value of Y also becomes large. In the separator of the present embodiment, the value of the parameter Y is preferably from 0.3 to 0.7, more preferably from 0.35 to 0.65. When the value of Y is 0.3 or more, curling is unlikely to occur. If the value of Y is 0.7 or less, high rate characteristics can be obtained.

又，上述數式(1)(2)中，耐熱絕緣層之厚度A’、A”及隔離層之總厚度C，可使用利用超音測厚儀(microgage)測定之值。又，耐熱絕緣層之孔隙率D(%)可使用構成耐熱絕緣層之各成分i中，每單位面積之成分i之質量Wi(g/cm2)、成分i之密度di(g/cm3)、耐熱絕緣層之厚度t(cm)，由下述數式(3)求得。又，兩面之耐熱絕緣層之孔隙率不同時，將該等之平均值作為孔隙率D(%)之值。 Further, in the above formula (1) (2), the thicknesses A' and A" of the heat resistant insulating layer and the total thickness C of the separator may be values measured by a microgage. Further, heat resistant insulation The porosity D (%) of the layer may be the mass Wi (g/cm 2 ) of the component i per unit area, the density di (g/cm 3 ) of the component i, and the heat-resistant insulation in each component i constituting the heat-resistant insulating layer. The thickness t (cm) of the layer is obtained by the following formula (3). Further, when the porosity of the heat-resistant insulating layers on both sides is different, the average value of the layers is taken as the value of the porosity D (%).

【數4】D=[1-(Σ Wi/di)×(1/t)]×100………(3) [Number 4] D=[1-(Σ Wi/di)×(1/t)]×100.........(3)

又，耐熱絕緣層3設於樹脂多孔質基體2之層合方向，亦即正極、負極及電解質層17層合之方向之兩面上。且，於樹脂多孔質基體2之兩面上形成之耐熱絕緣層3，如圖3所示，較好分別於耐熱絕緣層之對向面直接層合。再者，耐熱絕緣層3較好形成於樹脂多孔質基體2之兩面整面上。因此，如圖3所示，耐熱絕緣層3可由單層所成者，亦可由複數層所成者。且，耐熱絕緣層3由複數層所成時，亦可分別以不同材料形成。 Further, the heat-resistant insulating layer 3 is provided in the lamination direction of the resin porous substrate 2, that is, on both surfaces of the direction in which the positive electrode, the negative electrode, and the electrolyte layer 17 are laminated. Further, as shown in Fig. 3, the heat-resistant insulating layer 3 formed on both surfaces of the resin porous substrate 2 is preferably laminated directly on the opposite faces of the heat-resistant insulating layer. Further, the heat resistant insulating layer 3 is preferably formed on the entire surfaces of both sides of the resin porous substrate 2. Therefore, as shown in FIG. 3, the heat-resistant insulating layer 3 may be formed of a single layer or a plurality of layers. Further, when the heat resistant insulating layer 3 is formed of a plurality of layers, it may be formed of different materials.

以下，針對本實施形態之隔離層詳細加以說明。 Hereinafter, the separator of the present embodiment will be described in detail.

(樹脂多孔質基體) (Resin porous matrix)

至於樹脂多孔質基體2，可舉例有包含吸收保持電解質之有機樹脂之多孔性薄片、織布或不織布。樹脂多孔質基體中所含之有機樹脂，較好使用聚乙烯(PE)、聚丙烯(PP)等之聚烯烴；聚醯亞胺、芳醯胺；聚對苯二甲酸乙二酯(PET)等之聚酯。又，於樹脂多孔質基體上形成之細孔之孔徑平均值(平均細孔徑)較好為10nm~1μm。又，於樹脂多孔質基體上形成之細孔徑可利用例如氮氣吸附法求得。且，樹脂多孔質基體之厚度較好為1μm~200μm。再者，樹脂多孔質基體之孔隙率宜為20~90%。 As the resin porous substrate 2, a porous sheet, a woven fabric or a non-woven fabric containing an organic resin that absorbs and holds the electrolyte can be exemplified. The organic resin contained in the porous resin matrix is preferably a polyolefin such as polyethylene (PE) or polypropylene (PP); polyimine, arylamine; polyethylene terephthalate (PET). Etc. polyester. Further, the average pore diameter (average pore diameter) of the pores formed on the resin porous substrate is preferably from 10 nm to 1 μm . Further, the pore diameter formed on the resin porous substrate can be determined by, for example, a nitrogen gas adsorption method. Further, the thickness of the resin porous substrate is preferably from 1 μm to 200 μm . Further, the porosity of the resin porous substrate is preferably from 20 to 90%.

針對樹脂多孔質基體更詳細加以說明。可使用作為樹脂多孔質基體之多孔性薄片為以微多孔質之聚合物構成之微多孔質膜。至於該種聚合物，舉例有例如聚乙烯(PE)、聚丙烯(PP)等聚烯烴；PP/PE/PP之3層構造之層合體、聚醯亞胺、芳醯胺等。尤其，聚烯烴系微多孔質膜又對於有機溶劑之化學安定之性質，可將與電解液之反應性抑制在較低故而較佳。 The resin porous substrate will be described in more detail. The porous sheet which is a porous resin substrate can be used as a microporous film composed of a microporous polymer. As such a polymer, for example, a polyolefin such as polyethylene (PE) or polypropylene (PP); a laminate of a PP/PE/PP three-layer structure, polyimine, linaloamine or the like can be exemplified. In particular, the polyolefin-based microporous membrane is preferably chemically stable to an organic solvent, and the reactivity with the electrolytic solution can be suppressed to be low.

前述多孔性薄片厚度由於係依據用途而異故無法一概規定。然而，於車輛之馬達驅動用蓄電池之用途中，以單層或多層宜為4~60μm。前述多孔性薄片之微細孔徑通常為十nm左右之孔徑但較好最大為1μm以下。且，多孔性薄片之孔隙率宜為20~80%。 The thickness of the porous sheet described above cannot be specified because it is different depending on the use. However, in the use of a battery for driving a motor of a vehicle, it is preferably 4 to 60 μm in a single layer or a plurality of layers. The pore diameter of the porous sheet is usually about 10 nm or so, but preferably at most 1 μm . Further, the porosity of the porous sheet is preferably from 20 to 80%.

又，可作為樹脂多孔質基體使用之織布或不織布，可使用聚對苯二甲酸乙二酯(PET)等之聚酯；PP、PE等之 聚烯烴；聚醯亞胺、芳醯胺等。織布或不織布之鬆密度，只要為可藉由含浸之電解液獲得充分電池特性者即可，而無特別限制。織布或不織布之孔隙率較好為50~90%。再者，織布或不織布之厚度較好為5~200μm，最好為5~100μm。厚度若為5μm以上，則電解質之保持性良好，若為100μm以下，則電阻不易過度增大。 Further, as the woven or non-woven fabric used as the resin porous substrate, a polyester such as polyethylene terephthalate (PET), a polyolefin such as PP or PE, a polyimide, an arylamine or the like can be used. . The bulk density of the woven fabric or the non-woven fabric is not particularly limited as long as it can obtain sufficient battery characteristics by the impregnated electrolyte. The porosity of the woven or non-woven fabric is preferably from 50 to 90%. Further, the thickness of the woven or non-woven fabric is preferably from 5 to 200 μm , preferably from 5 to 100 μm . When the thickness is 5 μm or more, the electrolyte retainability is good, and if it is 100 μm or less, the electric resistance is not easily excessively increased.

樹脂多孔質基體之調製方法並無特別限制。樹脂多孔質基體為聚烯烴系微多孔質膜時，可藉由例如將聚烯烴溶解於溶劑中之後，擠出成薄片狀，隨後，去除溶劑，進行單軸延伸或雙軸延伸之方法而調製。又，作為溶劑，可使用鏈烷、液體鏈烷、鏈烷油、四氫萘、乙二醇、甘油、十氫萘等。 The method of preparing the resin porous substrate is not particularly limited. When the polyolefin porous substrate is a polyolefin-based microporous film, it can be prepared by, for example, dissolving a polyolefin in a solvent, extruding it into a sheet, and then removing the solvent to perform uniaxial stretching or biaxial stretching. . Further, as the solvent, an alkane, a liquid alkane, an alkane oil, tetrahydronaphthalene, ethylene glycol, glycerin or decalin can be used.

(耐熱絕緣層(耐熱絕緣多孔層)) (heat resistant insulating layer (heat resistant insulating porous layer))

本實施形態中，作為構成耐熱絕緣層之耐熱粒子之材質，係使用熔點或熱軟化點為150℃以上，較好為240℃以上之耐熱性高者。藉由使用此種耐熱性高的材質，即使電池內部溫度到達200℃前後，亦可有效防止隔離層之收縮。其結果，可防止電極間短路之誘發，故可獲得難以因溫度上升引起性能降低之電池。又，本說明書中，所謂「熱軟化點」意指經加熱之物質開始軟化、變形之溫度，意指維卡軟化溫度。又，耐熱粒子之熔點或熱軟化點之上限並未特別限制，例如可為1500℃以下。 In the present embodiment, the material of the heat-resistant particles constituting the heat-resistant insulating layer is a material having a melting point or a thermal softening point of 150 ° C or higher, preferably 240 ° C or higher. By using such a material having high heat resistance, even if the internal temperature of the battery reaches 200 ° C or so, the shrinkage of the separator can be effectively prevented. As a result, the induction of the short circuit between the electrodes can be prevented, so that it is difficult to reduce the performance due to the temperature rise. In the present specification, the term "thermal softening point" means a temperature at which a heated substance starts to soften and deform, and means a Vicat softening temperature. Further, the upper limit of the melting point or the thermal softening point of the heat-resistant particles is not particularly limited, and may be, for example, 1500 ° C or lower.

又，前述耐熱粒子具有電絕緣性，對於耐熱絕緣層之 製造時使用之溶劑或電解液為安定，進而於電池作動電壓範圍內不易氧化還原而為電化學安定。前述耐熱粒子可為有機粒子亦可為無機粒子，但基於安定性之觀點較好為無機粒子。又，前述耐熱粒子基於分散性之觀點較好為微粒子，可使用平均二次粒徑(中值粒徑，D50)為例如100nm~4μm，較好為300nm~3μm，更好為500nm~3μm之微粒子。又，平均二次粒徑(中值粒徑)可利用動態光散射法求得。且，前述耐熱粒子之形狀亦無特別限制，可為近似球狀之形狀，亦可為板狀、棒狀、針狀之形態。 Further, the heat-resistant particles have electrical insulating properties, and are stable to a solvent or an electrolytic solution used in the production of the heat-resistant insulating layer, and are not easily oxidized and reduced in the battery operating voltage range to be electrochemically stabilized. The heat-resistant particles may be organic particles or inorganic particles, but are preferably inorganic particles from the viewpoint of stability. Further, the heat-resistant particles are preferably fine particles from the viewpoint of dispersibility, and the average secondary particle diameter (median diameter, D50) can be, for example, 100 nm to 4 μm , preferably 300 nm to 3 μm , more preferably Microparticles of 500 nm to 3 μm . Further, the average secondary particle diameter (median diameter) can be obtained by a dynamic light scattering method. Further, the shape of the heat-resistant particles is not particularly limited, and may be a substantially spherical shape, and may be in the form of a plate, a rod, or a needle.

至於熔點或熱軟化點為150℃以上之無機粒子(無機粉末)並未特別限制。但，作為無機粒子，舉例有例如氧化鐵(FeO)、SiO2、Al2O3、鋁矽酸鹽(鋁矽酸鹽)、TiO2、BaTiO2、ZrO2等之無機氧化物；氮化鋁、氮化矽等之無機氮化物；氟化鈣、氟化鋇、硫酸鋇等之難溶性離子結晶；矽、金剛石等之共價鍵性結晶；蒙脫土等之黏土等之粒子。前述無機氧化物，亦可為勃母石、沸石、磷灰石、高嶺土、模來石、尖晶石、橄欖石、雲母等之源自礦物資源物質或該等之人造物等。又，前述無機粒子，亦可為於導電性材料之表面以具有電絕緣性之材料例如上述無機氧化物等被覆因而具有電絕緣性之粒子。作為導電性材料，可例示有金屬；SnO2、錫-銦氧化物(ITO)等之導電性氧化物；碳黑、石墨等之碳質材料等。其中，無機氧化物之粒子由於可容易地以分散漿料塗佈於樹脂多孔質基體上，故可藉由簡便方法製造隔離層而較佳。無機氧化物中， 最好為氧化鋁(Al2O3)、二氧化矽(SiO2)及鋁矽酸鹽(鋁矽酸鹽)。 The inorganic particles (inorganic powder) having a melting point or a thermal softening point of 150 ° C or more are not particularly limited. However, examples of the inorganic particles include inorganic oxides such as iron oxide (FeO), SiO 2 , Al 2 O 3 , aluminosilicate (aluminum silicate), TiO 2 , BaTiO 2 , and ZrO 2 ; Inorganic nitrides such as aluminum and tantalum nitride; insoluble ion crystals such as calcium fluoride, barium fluoride, and barium sulfate; covalently bonded crystals such as ruthenium and diamond; and clays such as montmorillonite. The inorganic oxide may be a mineral resource derived from boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine or mica, or the like. Further, the inorganic particles may be particles having electrical insulating properties such as the above-described inorganic oxide coated on the surface of the conductive material, such as the above-mentioned inorganic oxide. Examples of the conductive material include a metal; a conductive oxide such as SnO 2 or tin-indium oxide (ITO); a carbonaceous material such as carbon black or graphite. Among them, since the particles of the inorganic oxide can be easily applied to the resin porous substrate as a dispersion slurry, it is preferable to produce the separator by a simple method. Among the inorganic oxides, alumina (Al 2 O 3 ), cerium oxide (SiO 2 ) and aluminosilicate (aluminum silicate) are preferred.

至於熔點或熱軟化點為150℃以上之有機粒子(有機粉末)，可例示為交聯聚甲基丙烯酸甲酯、交聯聚苯乙烯、交聯聚二乙烯基苯、苯乙烯-二乙烯基苯共聚物交聯物、聚烯亞胺、三聚氰胺樹脂、酚樹脂、苯胍-甲醛縮合物等之各種交聯高分子粒子。又，作為有機粒子，可例示聚碸、聚丙烯腈、聚芳醯胺、聚乙縮醛、熱可塑性聚醯亞胺等之耐熱性高分子粒子。又，構成該等有機粒子之有機樹脂，亦可為上述例示之材料之混合物、改質物、衍生物、共聚物(無規共聚物、交替共聚物、嵌段共聚物、接枝共聚物)、交聯體(上述耐熱性高分子微粒子時)。其中，基於工業生產性、電化學安定性，宜使用聚甲基丙烯酸甲酯、聚芳醯胺之粒子作為有機粒子。藉由使用該等有機樹脂之粒子，由於可製作以樹脂為主體之隔離層，故獲得全體輕量之電池。 As the organic particles (organic powder) having a melting point or a thermal softening point of 150 ° C or more, it can be exemplified by cross-linked polymethyl methacrylate, crosslinked polystyrene, crosslinked polydivinylbenzene, styrene-divinyl Various crosslinked polymer particles such as a benzene copolymer crosslinked product, a polyalkylenimine, a melamine resin, a phenol resin, and a benzoquinone-formaldehyde condensate. Further, examples of the organic particles include heat-resistant polymer particles such as polyfluorene, polyacrylonitrile, polyarylamine, polyacetal, and thermoplastic polyimine. Further, the organic resin constituting the organic particles may be a mixture of the above-exemplified materials, a modified product, a derivative, a copolymer (a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer), Crosslinked body (in the case of the above heat resistant polymer fine particles). Among them, based on industrial productivity and electrochemical stability, particles of polymethyl methacrylate or polyarylamine are preferably used as the organic particles. By using the particles of the organic resin, since a resin-based separator can be produced, a light-weight battery can be obtained.

又，上述之耐熱粒子可單獨使用一種，亦可組合兩種以上使用。 Further, the above heat-resistant particles may be used singly or in combination of two or more.

至於使用上述耐熱粒子構成之耐熱絕緣層之厚度，係依據電池種類或用途而適當決定者，並未特別限制。但，作為耐熱絕緣層之厚度，較好例如於樹脂多孔質基體之兩面上形成之耐熱絕緣層之厚度合計為5~200μm左右。且，於電動汽車或油電混合汽車等之馬達驅動用蓄電池等之用途中，於樹脂多孔質基體之兩面上形成之耐熱絕緣層之 厚度合計為5~200μm，較好為5~20μm，更好為6~10μm。使耐熱絕緣層厚度在如此範圍內，可提高厚度方向(層合方向)之機械強度同時確保高輸出性。 The thickness of the heat-resistant insulating layer formed using the heat-resistant particles is appropriately determined depending on the type of the battery or the use, and is not particularly limited. However, as the thickness of the heat-resistant insulating layer, for example, the thickness of the heat-resistant insulating layer formed on both surfaces of the resin porous substrate is preferably about 5 to 200 μm . Further, in the application of a motor-driven battery such as an electric vehicle or a hybrid electric vehicle, the thickness of the heat-resistant insulating layer formed on both surfaces of the resin porous substrate is 5 to 200 μm , preferably 5 to 20 μ m, more preferably 6 to 10 μ m. When the thickness of the heat resistant insulating layer is within such a range, the mechanical strength in the thickness direction (lamination direction) can be improved while ensuring high output.

又，於樹脂多孔質基體之兩面上形成之耐熱絕緣層之厚度之比A’/A”只要以滿足數式(1)之方式設定即可，但較好為1.2以下，更好為1.1以下。亦即，耐熱絕緣層之厚度比A’/A”較好為1.0~1.2，更好為1.0~1.1。於樹脂多孔質基體之兩面上形成之耐熱絕緣層之厚度較好儘可能為相同。藉此，兩層耐熱絕緣層可均等地擠壓樹脂多孔質基體之兩面，可抑制隔離層捲曲。 Further, the ratio A'/A" of the thickness of the heat-resistant insulating layer formed on both surfaces of the resin porous substrate may be set as long as the formula (1) is satisfied, but is preferably 1.2 or less, more preferably 1.1 or less. That is, the thickness ratio A'/A" of the heat resistant insulating layer is preferably from 1.0 to 1.2, more preferably from 1.0 to 1.1. The thickness of the heat resistant insulating layer formed on both sides of the resin porous substrate is preferably as much as possible. Thereby, the two heat-resistant insulating layers can uniformly press both sides of the resin porous substrate, and the curl of the separator can be suppressed.

使用上述耐熱粒子構成之耐熱絕緣層之孔隙率並未特別限制，但基於離子傳導性之觀點，較好為40%以上，更好為50%以上。又，孔隙率若為40%以上，則電解質(電解液、電解質膠)之保持性高，可獲得高輸出電池。且，前述耐熱絕緣層之孔隙率較好為70%以下，更好為60%以下。前述耐熱絕緣層之孔隙率若為70%以下，則獲得充分的機械強度，防止因異物產生之短路的效果高。 The porosity of the heat-resistant insulating layer formed using the heat-resistant particles is not particularly limited, but is preferably 40% or more, more preferably 50% or more, from the viewpoint of ion conductivity. Moreover, when the porosity is 40% or more, the retention of the electrolyte (electrolyte or electrolyte) is high, and a high-output battery can be obtained. Further, the porosity of the heat resistant insulating layer is preferably 70% or less, more preferably 60% or less. When the porosity of the heat resistant insulating layer is 70% or less, sufficient mechanical strength is obtained, and the effect of preventing short circuit due to foreign matter is high.

再者，耐熱絕緣層中之上述耐熱粒子之含有率較好為90~100質量%，更好為95~100質量%。藉此，兩層耐熱絕緣層可均等地擠壓樹脂多孔質基體之兩面。 Further, the content of the heat-resistant particles in the heat-resistant insulating layer is preferably from 90 to 100% by mass, more preferably from 95 to 100% by mass. Thereby, the two heat-resistant insulating layers can uniformly press both sides of the resin porous substrate.

(隔離層之製造方法) (Method of manufacturing the isolation layer)

本實施形態之隔離層之製造方法並無特別限制。但作為製造方法，可使用例如於樹脂多孔質基體之兩面上，塗 佈含有熔點或熱軟化點為150℃以上之耐熱粒子之漿料狀耐熱絕緣層用組成物後，予以乾燥之方法。 The method for producing the separator of the present embodiment is not particularly limited. However, as a manufacturing method, for example, coating on both sides of a porous resin substrate can be used. The cloth contains a composition for a slurry-like heat-resistant insulating layer having a melting point or a heat-softening point of heat-resistant particles of 150 ° C or higher, and then dried.

耐熱絕緣層用組成物為將耐熱粒子分散於溶劑中者，依據需要亦可含有有機黏合劑。作為用以提高耐熱絕緣層之形狀安定性之有機黏合劑，舉例有例如羧甲基纖維素、羥乙基纖維素、聚乙烯醇、聚乙烯縮丁醛、聚乙烯吡咯烷酮等。含有有機黏合劑時，前述有機黏合劑之使用量相對於前述耐熱粒子與前述有機黏合劑之合計質量，較好為10質量%以下，更好為5質量%以下。作為溶劑只要可均一分散耐熱粒子者即無特別限制。但，作為溶劑，舉例有例如水；甲苯等之芳香族烴；四氫呋喃等之呋喃類；甲基乙基酮、甲基異丁基酮、丙酮等酮類；N-甲基吡咯烷酮；二甲基乙醯胺；二甲基甲醯胺；二甲基亞碸；乙酸乙酯等。該等溶劑中，基於控制界面張力之目的，亦可適當添加乙二醇、丙二醇、單甲機乙酸酯等。尤其使用無機氧化物粒子作為前述耐熱粒子時使用水作為溶劑而製作水分散漿料時，可簡便地製作耐熱絕緣層。又，耐熱絕緣層組成物較好調製為固體成分濃度為30~60質量%。 The composition for a heat resistant insulating layer is a material which disperses heat resistant particles in a solvent, and may contain an organic binder as needed. Examples of the organic binder for improving the shape stability of the heat resistant insulating layer include carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, polyvinyl butyral, and polyvinyl pyrrolidone. When the organic binder is used, the amount of the organic binder to be used is preferably 10% by mass or less, more preferably 5% by mass or less based on the total mass of the heat-resistant particles and the organic binder. The solvent is not particularly limited as long as it can uniformly disperse the heat-resistant particles. However, examples of the solvent include, for example, water; aromatic hydrocarbons such as toluene; furans such as tetrahydrofuran; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and acetone; N-methylpyrrolidone; Acetamide; dimethylformamide; dimethyl hydrazine; ethyl acetate and the like. Among these solvents, ethylene glycol, propylene glycol, monomethyl acetate or the like may be appropriately added for the purpose of controlling the interfacial tension. In particular, when inorganic oxide particles are used as the heat-resistant particles, water is used as a solvent to prepare a water-dispersed slurry, and a heat-resistant insulating layer can be easily produced. Further, the heat resistant insulating layer composition is preferably prepared so that the solid content concentration is 30 to 60% by mass.

於前述樹脂多孔質基體上塗佈耐熱絕緣層用組成物時之單位面積重並未特別限制，但較好為5~20g/m2，更好為9~13 g/m2。又，該情況下之所謂「單位面積重」意指樹脂多孔質基體之每單位面積中耐熱絕緣層用組成物之重量(g/m2)。若為上述範圍，可獲得具有適當孔隙率及厚度之耐熱絕緣層。塗佈方法亦未特別限制，舉例有例如刮刀塗 佈法、凹版塗佈法、網版印刷法、馬亞棒塗佈法、模嘴塗佈法、逆轉輥塗佈法、噴墨法、噴霧法、輥塗佈法等。 The weight per unit area when the composition for a heat resistant insulating layer is applied to the resin porous substrate is not particularly limited, but is preferably 5 to 20 g/m 2 , more preferably 9 to 13 g/m 2 . In this case, the "weight per unit area" means the weight (g/m 2 ) of the composition for a heat resistant insulating layer per unit area of the resin porous substrate. If it is the above range, a heat resistant insulating layer having an appropriate porosity and thickness can be obtained. The coating method is also not particularly limited, and examples thereof include, for example, a doctor blade coating method, a gravure coating method, a screen printing method, a Maya bar coating method, a die coating method, a reverse roll coating method, an inkjet method, and a spray. Method, roll coating method, and the like.

使塗佈後之耐熱絕緣層用組成物乾燥之方法並未特別限制，但例如可使用溫風乾燥法。乾燥溫度為例如30~80℃，乾燥時間為例如2秒至50小時。 The method of drying the composition for the heat-resistant insulating layer after coating is not particularly limited, but for example, a warm air drying method can be used. The drying temperature is, for example, 30 to 80 ° C, and the drying time is, for example, 2 seconds to 50 hours.

如此所得隔離層總厚度並未特別限制，但通常若為5~30μm左右即可使用。為獲得小型電池，較好在可確保作為電解質層功能之範圍內儘量薄。因此，為薄膜化並有助於電池輸出之提高，隔離層總厚度較好為20~30μm，更好為20~25μm。 The total thickness of the separator thus obtained is not particularly limited, but it is usually about 5 to 30 μm . In order to obtain a small battery, it is preferable to be as thin as possible within a range that can ensure the function as an electrolyte layer. Therefore, in order to thin the film and contribute to the improvement of the battery output, the total thickness of the separator is preferably 20 to 30 μm , more preferably 20 to 25 μm .

作為電解質層，若為使用本實施形態之隔離層所形成者，即無特別限制。亦即，本實施形態之電解質層為具有上述隔離層及於隔離層之樹脂多孔質基體及耐熱絕緣層內部所含有之電解質者。又，保持於電解質層中之電解質含有鋰離子且較好鋰離子傳導性優異。 The electrolyte layer is not particularly limited as long as it is formed by using the separator of the present embodiment. In other words, the electrolyte layer of the present embodiment is one having the separator and the resin porous substrate and the electrolyte contained in the heat-resistant insulating layer in the separator. Further, the electrolyte held in the electrolyte layer contains lithium ions and is preferably excellent in lithium ion conductivity.

具體而言，作為電解質層，可使用含有離子傳導性優異之電解液之隔離層。且，亦可利用將膠體電解質等含浸、塗佈、噴霧(等)於隔離層中形成之電解質層。 Specifically, as the electrolyte layer, a separator containing an electrolytic solution excellent in ion conductivity can be used. Further, an electrolyte layer formed by impregnating, coating, spraying (etc.) the colloidal electrolyte or the like into the separator may be used.

(a)含有電解液之隔離層 (a) Isolation layer containing electrolyte

可浸染入本實施形態之隔離層中之電解液中，作為電解質，可使用LiClO4、LiAsF6、LiPF5、LiBOB、LiCF3SO3及Li(CF3SO2)2N之至少一種。又，作為電解液之溶劑，可使用如碳酸伸乙酯(EC)、碳酸伸丙酯、碳酸二乙酯(DEC)、碳酸二甲酯、碳酸甲酯乙酯、1,2-二甲 氧基乙烷、1,2-二乙氧基乙烷、四氫呋喃、1,3-二氧代環戊烷及γ-丁內酯之醚類中之至少一種。接著，將前述電解質溶解於前述溶劑中，較好將電解質濃度調整為0.5~2M而使用。但，本發明並無限定於此。 In the electrolytic solution which can be impregnated into the separator of the present embodiment, at least one of LiClO 4 , LiAsF 6 , LiPF 5 , LiBOB, LiCF 3 SO 3 and Li(CF 3 SO 2 ) 2 N can be used as the electrolyte. Further, as the solvent of the electrolytic solution, for example, ethyl carbonate (EC), propyl carbonate, diethyl carbonate (DEC), dimethyl carbonate, ethyl methyl carbonate, 1,2-dimethoxy can be used. At least one of an ethyl ether, 1,2-diethoxyethane, tetrahydrofuran, 1,3-dioxocyclopentane, and an ether of γ-butyrolactone. Next, the electrolyte is dissolved in the solvent, and the electrolyte concentration is preferably adjusted to 0.5 to 2 M. However, the present invention is not limited to this.

作為上述隔離層，由於可使用已說明之本實施形態之隔離層，故於此處省略說明。 As the above-mentioned spacer layer, since the spacer layer of the present embodiment described above can be used, the description thereof is omitted here.

藉由含浸等保持於上述隔離層中之電解液量，只要在隔離層之保液能力範圍內含浸、塗佈等即可，但亦可超過該保液能力予以含浸。此係由於例如於雙極型電池時，為防止於電解質密封部中注入樹脂而自電解質層滲出電解液，故若為該電解質層之可於隔離層中保液之範圍則可含浸。同樣，於非雙電極型電池時，為防止將電池成分封裝入電池外裝材而自電池外裝材滲出電解液，故若可於電池外裝材中保液之範圍則可含浸。該電解液可利用真空注液法注液後，完全予以密封等之以往公知方法將電解液含浸於隔離層中。 The amount of the electrolytic solution held in the separator by impregnation or the like may be impregnated, coated, or the like within the range of the liquid retaining ability of the separator, but may be impregnated beyond the liquid retaining ability. This is because, for example, in the case of a bipolar battery, the electrolyte is oozing out from the electrolyte layer in order to prevent the resin from being injected into the electrolyte sealing portion, so that the electrolyte layer can be impregnated in the range of liquid retention in the separator. Similarly, in the case of a non-two-electrode type battery, in order to prevent the battery component from being encapsulated in the battery exterior material, the electrolyte is exuded from the battery exterior material, so that it can be impregnated in the range of liquid retention in the battery exterior material. This electrolyte solution can be impregnated into the separator by a conventionally known method such as liquid injection by a vacuum injection method.

(b)膠體電解質層 (b) Colloidal electrolyte layer

本發明之膠體電解質層為藉由將膠體電解質含浸、塗佈(等)於本實施形態之隔離層中而保持者。 The colloidal electrolyte layer of the present invention is retained by impregnating, coating (or the like) the colloidal electrolyte in the separator of the present embodiment.

膠體電解質層具有於由離子傳導性聚合物所成之基質聚合物中注入上述液體電解質(電解液)之構成。作為基質聚合物使用之離子傳導性聚合物舉例有例如聚環氧乙烷(PEO)、聚環氧丙烷(PPO)及該等之共聚物等。於此種聚環氧烷系聚合物中可良好地溶解鋰鹽等之電解質鹽。 The colloidal electrolyte layer has a configuration in which the above liquid electrolyte (electrolyte) is injected into a matrix polymer made of an ion conductive polymer. Examples of the ion conductive polymer used as the matrix polymer include polyethylene oxide (PEO), polypropylene oxide (PPO), and the like. An electrolyte salt such as a lithium salt can be satisfactorily dissolved in such a polyalkylene oxide-based polymer.

膠體電解質中之上述液體電解質(電解液)之比例，並未特別限制，但由離子傳導度之觀點觀之，宜成為數質量%~98質量%。本實施形態中，電解液之比例為70質量%以上之電解液較多之膠體電解質特別有效。 The ratio of the above liquid electrolyte (electrolyte) in the colloidal electrolyte is not particularly limited, but it is preferably from several mass% to 98% by mass from the viewpoint of ion conductivity. In the present embodiment, a colloidal electrolyte having a large electrolytic solution in which the ratio of the electrolytic solution is 70% by mass or more is particularly effective.

膠體電解質之基質聚合物可藉由形成交聯構造而展現優異之機械強度。形成交聯構造可使用適當聚合起始劑，對高分子電解質形成用之聚合性聚合物進行聚合處理即可。至於聚合處理，可舉例熱聚合、紫外線聚合、輻射線聚合、電子束聚合等。至於聚合性聚合物，可使用例如PEO或PPO。 The matrix polymer of the colloidal electrolyte can exhibit excellent mechanical strength by forming a crosslinked structure. The crosslinked structure may be formed by polymerizing a polymerizable polymer for forming a polymer electrolyte using a suitable polymerization initiator. As the polymerization treatment, thermal polymerization, ultraviolet polymerization, radiation polymerization, electron beam polymerization, or the like can be exemplified. As the polymerizable polymer, for example, PEO or PPO can be used.

電解質層之厚度並未特別限定，基本上，為與本實施形態之隔離層厚度略相等或稍厚之程度。電解質層厚度通常若為5~30μm左右即可使用。 The thickness of the electrolyte layer is not particularly limited, and is basically equal to or slightly thicker than the thickness of the separator in the present embodiment. The thickness of the electrolyte layer is usually about 5 to 30 μm .

又，本發明中，於上述電解質層中之電解質中，只要在不損及本發明作用效果之範圍內，亦可含有以往習知各種添加劑。 Further, in the present invention, the electrolyte in the electrolyte layer may contain various conventionally known additives as long as the effects of the present invention are not impaired.

[集電板及引線] [Collector board and leads]

為將電流取出於電池外部，亦可使用集電板。集電板係與集電體或引線電性連接，並取出至電池外裝材的層合薄片外部。 A collector plate can also be used to take current out of the battery. The collector plate is electrically connected to the current collector or the lead wire and taken out to the outside of the laminated sheet of the battery exterior material.

構成集電板之材料並未特別限制，可使用作為鋰離子蓄電池之集電板而公知之高導電性材料。至於集電板之構成材料較好為例如鋁、銅、鈦、鎳、不鏽鋼(SUS)、該 等之合金等之金屬材料。至於集電板之構成材料，由輕量、耐蝕性、高導電性之觀點而言，最好為鋁、銅等。且，正極集電板及負極集電板可使用相同材質，亦可使用不同材質。 The material constituting the current collector plate is not particularly limited, and a highly conductive material known as a current collector plate of a lithium ion battery can be used. The constituent material of the current collector plate is preferably, for example, aluminum, copper, titanium, nickel, stainless steel (SUS), Metal materials such as alloys. The constituent material of the current collector plate is preferably aluminum, copper or the like from the viewpoint of light weight, corrosion resistance and high electrical conductivity. Moreover, the positive electrode current collector plate and the negative electrode current collector plate can be made of the same material or different materials.

關於正極端子引線及負極端子引線亦可依需要使用。正極端子引線及負極端子引線之材料，可使用於公知鋰離子蓄電池中所用之端子引線。又，自電池外裝材29取出之部分較好利用耐熱絕緣性之熱收縮管被覆。藉此，藉由與周邊機器或配線等接觸而漏電，可防止對製品(例如汽車零件，尤其是電子機器)帶來影響。 The positive terminal lead and the negative terminal lead can also be used as needed. The material of the positive electrode terminal lead and the negative electrode terminal lead can be used for a terminal lead used in a known lithium ion secondary battery. Further, the portion taken out from the battery exterior material 29 is preferably covered with a heat-shrinkable tube having heat-resistant insulation properties. Thereby, leakage by contact with peripheral equipment, wiring, or the like can prevent the influence on products (for example, automobile parts, especially electronic equipment).

[電池外裝材] [Battery exterior material]

電池外裝材29可使用公知金屬罐盒。且，作為電池外裝材29，可覆蓋發電要件，可使用利用包含鋁之層合膜之袋狀盒。至於層合膜，可使用例如將PP、鋁、尼龍依序層合而成之3層構造之膜等，但不限於此。基於高輸出化或冷卻性能優異、可較好地利用於EV、HEV用之大型機器用電池之觀點而言，宜為層合膜。 As the battery exterior material 29, a known metal can can be used. Further, as the battery exterior material 29, a power generation element can be covered, and a bag-shaped case using a laminated film containing aluminum can be used. As the laminated film, for example, a film having a three-layer structure in which PP, aluminum, and nylon are laminated in this order can be used, but is not limited thereto. It is preferable that it is a laminated film from the viewpoint of being excellent in high-output and cooling performance, and can be utilized suitably for the battery for large-sized machines for EV and HEV.

又，上述鋰離子蓄電池可利用以往公知之製造方法製造。 Further, the lithium ion secondary battery can be produced by a conventionally known production method.

[鋰離子蓄電池之外觀構成] [Appearance of Lithium Ion Battery]

圖4為顯示平板層合型鋰離子蓄電池之外觀之立體圖。 Fig. 4 is a perspective view showing the appearance of a flat laminated lithium ion battery.

如圖4所示，層合型電池10具有長方形狀之扁平形狀，自其兩側部引出用以取出電力之正極集電板25及負極集電板27。發電要件21利用層合型電池10之電池外裝材29予以包裹，進而使電池外裝材29周圍熱熔著。又，發電要件21係以將正極集電板25及負極集電板27引出至外部之狀態予以密封。發電要件21為使以圖1所示之正極(正極活性物質層13)、電解質層17及負極(負極活性物質層15)構成之單電池層(單電池)19以覆數個層合而成者。 As shown in FIG. 4, the laminated battery 10 has a rectangular flat shape, and a positive electrode current collector plate 25 and a negative electrode current collector plate 27 for taking out electric power are taken out from both side portions. The power generation element 21 is wrapped by the battery exterior material 29 of the laminated battery 10, and further, the battery exterior material 29 is thermally fused around. Moreover, the power generation element 21 is sealed in a state in which the positive electrode current collector plate 25 and the negative electrode current collector plate 27 are taken out to the outside. The power generation element 21 is formed by laminating a plurality of battery cells (single cells) 19 including a positive electrode (positive electrode active material layer 13), an electrolyte layer 17, and a negative electrode (negative electrode active material layer 15) shown in FIG. By.

又，圖4所示之正極集電板25及負極集電板自電池外裝材29之引出亦無特別限制。可將正極集電板25及負極集電板27於同一邊引出。且，正極集電板25及負極集電板27亦可各分為複數，自各邊引出。亦即，正極集電板25及負極集電板自電池外裝材29之引出並不限於圖4所示者。 Further, the positive electrode current collector plate 25 and the negative electrode current collector plate shown in FIG. 4 are also not particularly limited in their extraction from the battery exterior material 29. The positive electrode current collector plate 25 and the negative electrode current collector plate 27 can be taken out on the same side. Further, the positive electrode current collector plate 25 and the negative electrode current collector plate 27 may be divided into plural numbers and taken out from the respective sides. That is, the extraction of the positive electrode current collector plate 25 and the negative electrode current collector plate from the battery exterior material 29 is not limited to that shown in FIG.

又，上述實施形態中，作為電裝置係例示鋰離子蓄電池。然而，不限於此，可適用於其他類型之蓄電池，進而亦可液用於原電池。且不僅電池，亦可應用於電容器。 Further, in the above embodiment, a lithium ion battery is exemplified as an electric device. However, it is not limited thereto, and can be applied to other types of batteries, and can also be used for a primary battery. And not only batteries, but also capacitors.

[實施例] [Examples]

以下基於實施例對本發明詳細說明。又，本發明之技術範圍並不僅限定於該等實施例。 The invention is described in detail below based on the examples. Further, the technical scope of the present invention is not limited to the embodiments.

[實施例1] [Example 1]

利用刮刀塗佈器，於樹脂多孔質基體的聚乙烯(PE)微多孔膜之兩面上塗佈耐熱絕緣層用組成物的鋁矽酸鹽微粒子之分散體。此處，聚乙烯微多孔膜之膜厚為18.9μm，孔隙率為42%。且，鋁矽酸鹽微粒子之平均二次粒徑為1μm，熔點為1000℃以上。再者，鋁矽酸鹽微粒子之水分散體之固體成分濃度為40質量%。隨後，經熱風乾燥形成耐熱絕緣層，製作附有耐熱絕緣層之隔離層。該附有耐熱絕緣層之隔離層以寬度200mm形成輥狀。 A dispersion of aluminosilicate fine particles of a composition for a heat-resistant insulating layer was applied to both sides of a polyethylene (PE) microporous film of a resin porous substrate by a doctor blade applicator. Here, the polyethylene microporous membrane has a film thickness of 18.9 μm and a porosity of 42%. Further, the aluminosilicate fine particles have an average secondary particle diameter of 1 μm and a melting point of 1000 ° C or more. Further, the solid content concentration of the aqueous dispersion of the aluminosilicate fine particles was 40% by mass. Subsequently, a heat resistant insulating layer was formed by hot air drying to form an insulating layer with a heat resistant insulating layer. The separator having the heat resistant insulating layer was formed into a roll shape with a width of 200 mm.

耐熱絕緣層係以使單面厚度為2.8μm以上之方式塗佈，但可以厚側為3.1μm、薄側為2.5μm予以最後加工。所得附有耐熱絕緣層之隔離層總厚度為24.5μm，耐熱絕緣層之孔隙率為47%。 The heat-resistant insulating layer is applied in such a manner that the thickness of one side is 2.8 μm or more, but it can be finally processed by a thickness of 3.1 μm and a thin side of 2.5 μm . The resulting separator having a heat-resistant insulating layer had a total thickness of 24.5 μm , and the heat-resistant insulating layer had a porosity of 47%.

[實施例2~12、比較例1~4] [Examples 2 to 12, Comparative Examples 1 to 4]

與實施例1同樣，製作具有表1所示之樹脂多孔質基體、耐熱絕緣層之隔離層。 In the same manner as in Example 1, a separator having a resin porous substrate and a heat resistant insulating layer shown in Table 1 was produced.

但，實施例2、3、6及11及比較例2中，使用聚丙烯(PP)微多孔膜(孔隙率55%)代替聚乙烯微多孔膜作為樹脂多孔質基體。 However, in Examples 2, 3, 6 and 11 and Comparative Example 2, a polypropylene (PP) microporous film (porosity: 55%) was used instead of the polyethylene microporous film as a resin porous substrate.

又，實施例4、5、7、9及10及比較例3中，使用聚乙烯(PE)微多孔膜(孔隙率52%)代替聚乙烯微多孔膜(孔隙率42%)作為樹脂多孔質基體。 Further, in Examples 4, 5, 7, 9, and 10 and Comparative Example 3, a polyethylene (PE) microporous film (porosity: 52%) was used instead of the polyethylene microporous film (porosity: 42%) as a resin porous material. Matrix.

實施例8中，使用聚對苯二甲酸乙二酯(PET)製不織布代替聚乙烯微多孔膜作為樹脂多孔質基體。且，聚對 苯二甲酸乙二酯製不織布膜厚為11.1μm，孔隙率為48%。 In Example 8, a polyethylene terephthalate (PET) nonwoven fabric was used instead of the polyethylene microporous film as a resin porous substrate. Further, the polyethylene terephthalate non-woven fabric had a film thickness of 11.1 μm and a porosity of 48%.

比較例1、4及5中，使用聚乙烯(PE)微多孔膜(孔隙率42%)作為樹脂多孔質基體。 In Comparative Examples 1, 4 and 5, a polyethylene (PE) microporous film (porosity: 42%) was used as the resin porous substrate.

實施例2~7、實施例10及11以及比較例2及3中，使用高純度氧化鋁粒子取代實施例1之鋁矽酸鹽作為耐熱粒子。且高純度氧化鋁粒子之平均二次粒徑為1.5μm，熔點為1000℃以上。 In Examples 2 to 7, Examples 10 and 11, and Comparative Examples 2 and 3, high-purity alumina particles were used in place of the aluminosilicate of Example 1 as heat-resistant particles. Further, the high-purity alumina particles have an average secondary particle diameter of 1.5 μm and a melting point of 1000 ° C or more.

實施例8中，使用膠體二氧化矽粒子之甲基乙基酮分散體取代實施例1之鋁矽酸鹽水分散體。且膠體二氧化矽粒子之平均二次粒徑為0.4μm，熔點為1000℃以上。又，甲基乙基酮分散體之固體成分濃度為30質量%。 In Example 8, the aluminosilicate aqueous dispersion of Example 1 was replaced with a methyl ethyl ketone dispersion of colloidal cerium oxide particles. Further, the colloidal cerium oxide particles have an average secondary particle diameter of 0.4 μm and a melting point of 1000 ° C or more. Further, the solid content concentration of the methyl ethyl ketone dispersion was 30% by mass.

實施例9中，使用交聯聚丙烯酸甲酯粒子取代實施例1之鋁矽酸鹽水分散體。且交聯聚丙烯酸甲酯粒子之平均二次粒徑為1μm，熱軟化點為160℃。 In Example 9, the crosslinked polymethyl acrylate particles were used in place of the aluminosilicate aqueous dispersion of Example 1. Further, the crosslinked polymethyl acrylate particles had an average secondary particle diameter of 1 μm and a thermal softening point of 160 °C.

實施例12中，使用芳香族聚醯胺(芳醯胺)樹脂之NMP分散體作為耐熱絕緣層用組成物，添加用以成為多孔質層之乙二醇。 In Example 12, an NMP dispersion of an aromatic polyamine (arylamine) resin was used as a composition for a heat-resistant insulating layer, and ethylene glycol to form a porous layer was added.

[比較例5] [Comparative Example 5]

除於樹脂多孔質基體單面上塗佈耐熱絕緣層以外，與實施例1同樣製作隔離層。 A separator was produced in the same manner as in Example 1 except that the heat-resistant insulating layer was applied to one surface of the porous resin substrate.

所得實施例1~12及比較力1~5之隔離層中之耐熱絕緣層厚度A’、A”(μm)、總厚度C(μm)及耐熱絕緣 層之孔隙率D(%)概述於表1。 Summary of the thicknesses A', A" ( μm ), total thickness C ( μm ) of the heat-resistant insulating layer in the isolation layers of Examples 1 to 12 and Comparative Forces 1 to 5, and the porosity D (%) of the heat-resistant insulating layer In Table 1.

[捲曲高度] [Curl Height]

各實施例及比較例所製作之隔離層之捲曲高度藉以下順序測定。首先，如圖5所示，自隔離層之輥，切出略正方形之隔離層，載置於水平面上之後，以除電刷撫觸兩次除去靜電。隨後，於圖5之A~H之8處，測定在60秒時自水平面上浮之高度，其最大值作為捲曲高度(mm)。於捲成圓時，解開捲曲部分向上方伸展，將其高度作為測定值。 The crimp height of the separator produced in each of the examples and the comparative examples was measured in the following order. First, as shown in Fig. 5, a strip of a square shape is cut out from the roll of the spacer layer, and after being placed on a horizontal surface, the static electricity is removed by touching the brush twice. Subsequently, at 8 o'clock of A to H of Fig. 5, the height from the horizontal surface at 60 seconds was measured, and the maximum value thereof was taken as the curl height (mm). When the roll is rounded, the unwound portion is stretched upward, and the height is taken as a measured value.

[電池評價] [Battery evaluation]

分別準備鋁箔作為正極集電體，銅箔作為負極集電體。使用鈷鎳錳酸鋰(LiNi0.33Co0.33Mn0.33O2)作為正極活性物質調製正極活性物質漿料。另一方面，使用人造石墨作為負極活性物質調製負極活性物質漿料。將正極活性物質漿料及負極活性物質漿料分別塗佈於正極集電體之鋁箔及負極集電體之銅箔上，乾燥後進行輥壓製，製作正極及負極。於上述製作之正極、負極間夾入各實施例、比較例製作之隔離層，注入非水電解液，封裝於層合薄片內，製作評價用電池。又，至於非水電解液，係使用於碳酸伸乙酯：碳酸乙酯甲酯=1：2(體積比)之混合溶劑中，溶解作為溶質之LiPF6使濃度成為1.0ml/L者。 Aluminum foil was prepared as a positive electrode current collector, and copper foil was used as a negative electrode current collector. A positive electrode active material slurry was prepared using lithium cobalt nickel manganese oxide (LiNi 0.33 Co 0.33 Mn 0.33 O 2 ) as a positive electrode active material. On the other hand, artificial graphite is used as a negative electrode active material to prepare a negative electrode active material slurry. The positive electrode active material slurry and the negative electrode active material slurry were applied onto the aluminum foil of the positive electrode current collector and the copper foil of the negative electrode current collector, dried, and then subjected to roll pressing to prepare a positive electrode and a negative electrode. The separator prepared in each of the examples and the comparative examples was sandwiched between the positive electrode and the negative electrode prepared above, and a non-aqueous electrolyte solution was poured thereinto and sealed in a laminated sheet to prepare a battery for evaluation. Further, the non-aqueous electrolyte solution was used in a mixed solvent of ethyl carbonate: ethyl methyl carbonate = 1:2 (volume ratio), and LiPF 6 as a solute was dissolved to have a concentration of 1.0 ml/L.

電池製作後，進行初次充放電，測定電池電容。又， 初次放電電容為20mAh。接著，針對本電池，測定於4.0mA之放電電容及在50mA之放電電容，其比(於50mA之放電電容/於4.0mA之放電電容)作為速率特性(速率比)(%)。 After the battery is fabricated, the first charge and discharge are performed, and the battery capacity is measured. also, The initial discharge capacitance is 20mAh. Next, with respect to the battery, a discharge capacitance of 4.0 mA and a discharge capacitance of 50 mA were measured, and the ratio (discharge capacitance at 50 mA / discharge capacitance at 4.0 mA) was taken as a rate characteristic (rate ratio) (%).

各實施例及比較例之速率特性結果示於表1。且，參數X與捲曲高度之關係示於圖6，參數Y與捲曲高度及速率特性之關係示於圖7。 The rate characteristic results of the respective examples and comparative examples are shown in Table 1. Further, the relationship between the parameter X and the curl height is shown in Fig. 6, and the relationship between the parameter Y and the curl height and rate characteristics is shown in Fig. 7.

實施例1~12製作之隔離層之參數X為0.15以上之值。而且，實施例1~12任一者之捲曲高度為5mm以下，以平板連續層合機層合時亦無問題，連續獲得良品。此處，平板連續層合機係包含重覆數十次之以熱刀切斷、以多孔吸附墊搬送、及以4點夾具之層合之步驟，確認可不使端部折入而層合。且，包含以熱刀之切斷、以多孔吸附墊搬送、及以4點夾具之層合之步驟以3秒左右進行。 The parameter X of the separator produced in Examples 1 to 12 was a value of 0.15 or more. Further, in any of Examples 1 to 12, the crimp height was 5 mm or less, and there was no problem in lamination with a flat continuous laminator, and a good product was continuously obtained. Here, the continuous plate laminating machine includes a step of cutting with a hot knife for several dozen times, transporting with a porous adsorption pad, and laminating with a four-point jig, and confirming that the end portions can be folded without being folded. Further, the step of cutting with a hot knife, transporting with a porous adsorption pad, and laminating with a 4-point jig was carried out for about 3 seconds.

比較例1~4之隔離層，於平板連續層合機中，於朝電極上搬送隔離層中，隔離層屢次捲起。因此，作成層合體時會以以踩入隔離層之狀態層合，而變無法使用。尤其，於單面塗佈之比較例5中，在切割之時點立即捲曲，本身無法搬送。 The separators of Comparative Examples 1 to 4 were transferred to the separator in the continuous layer laminator, and the separator was repeatedly rolled up. Therefore, when the laminate is formed, it is laminated in a state in which the separator is stepped on, and it becomes unusable. In particular, in Comparative Example 5 in which single-side coating was applied, it was immediately curled at the time of cutting, and it was not transportable by itself.

關於速率特性，實施例1~9所製作之隔離層，參數Y為0.3~0.7，獲得超過85%之充分輸出。另一方面，參數Y之值超過0.7之實施例10~12，速率特性低於85%，作為製品之性能稍不充分。 Regarding the rate characteristics, the isolation layers produced in Examples 1 to 9 had a parameter Y of 0.3 to 0.7, and a sufficient output of more than 85% was obtained. On the other hand, in Examples 10 to 12 in which the value of the parameter Y exceeded 0.7, the rate characteristic was less than 85%, and the performance as a product was slightly insufficient.

由以上結果，可知藉由調節耐熱絕緣層厚度相對於隔離層總厚度，使兩面耐熱絕緣層厚度均衡，可抑制捲曲發生。 From the above results, it is understood that by adjusting the thickness of the heat-resistant insulating layer with respect to the total thickness of the separator, the thickness of the heat-resistant insulating layer on both sides is equalized, and curling can be suppressed.

再者可知除上述條件以外，藉由調整耐熱絕緣層厚度及孔隙率，而同時獲得輸出特性高之電池。 Further, it is understood that, in addition to the above conditions, by adjusting the thickness and porosity of the heat-resistant insulating layer, a battery having high output characteristics can be obtained at the same time.

日本專利申請號特願2011-138983號(申請日：2011年6月22日)之全部內容於本文被引用。 The entire contents of Japanese Patent Application No. 2011-138983 (filing date: June 22, 2011) are hereby incorporated by reference.

以上，雖依據實施例說明本發明內容，但本發明不限 定於該等記載，而可進行各種變形及改良，此為熟知本技藝者當可理解。 Although the content of the present invention has been described above based on the embodiments, the present invention is not limited thereto. Various modifications and improvements are possible in light of the above description, which will be understood by those skilled in the art.

[產業上之可能利用性] [Industry possible use]

本發明之附有耐熱絕緣層之隔離層，藉由抑制兩面之耐熱絕緣層厚度及總厚度，而改善兩面之耐熱絕緣層之收縮應力。且，樹脂多孔質基體之內部應力與耐熱絕緣層之收縮應力之平衡獲得改善。因此，層合時難以發生捲曲，可穩定地製造信賴性高的電裝置。 The isolating layer with a heat-resistant insulating layer of the present invention improves the shrinkage stress of the heat-resistant insulating layers on both sides by suppressing the thickness and total thickness of the heat-resistant insulating layers on both sides. Further, the balance between the internal stress of the resin porous substrate and the shrinkage stress of the heat resistant insulating layer is improved. Therefore, it is difficult to cause curling at the time of lamination, and it is possible to stably manufacture an electric device having high reliability.

1‧‧‧附有耐熱絕緣層之隔離層(隔離層) 1‧‧‧Separation layer (isolation layer) with heat-resistant insulating layer

2‧‧‧樹脂多孔質基體層 2‧‧‧Resin porous matrix layer

3‧‧‧耐熱絕緣層 3‧‧‧Heat-resistant insulation

4‧‧‧正極 4‧‧‧ positive

5‧‧‧負極 5‧‧‧negative

10‧‧‧層合型電池(鋰離子蓄電池) 10‧‧‧Laminated battery (lithium ion battery)

11‧‧‧正極集電體 11‧‧‧ positive current collector

12‧‧‧負極集電體 12‧‧‧Negative current collector

13‧‧‧正極活性物質層 13‧‧‧positive active material layer

15‧‧‧負極活性物質層 15‧‧‧Negative active material layer

17‧‧‧電解質層 17‧‧‧ electrolyte layer

19‧‧‧單電池層 19‧‧‧Single cell layer

21‧‧‧發電要件 21‧‧‧Power generation requirements

25‧‧‧正極集電板 25‧‧‧ positive current collector board

27‧‧‧負極集電板 27‧‧‧Negative current collector board

29‧‧‧電池外裝材(層合膜) 29‧‧‧Battery exterior material (laminated film)

圖1為示意性表示本發明一實施形態之平板層合型之非雙極型鋰離子蓄電池之剖面概略圖。 Fig. 1 is a schematic cross-sectional view showing a non-bipolar lithium ion secondary battery of a flat laminated type according to an embodiment of the present invention.

圖2為表示本發明一實施形態之附有耐熱絕緣層之隔離層之概略示意圖。 Fig. 2 is a schematic view showing an insulating layer with a heat-resistant insulating layer according to an embodiment of the present invention.

圖3為示意性表示本發明一實施形態之附有耐熱絕緣層之隔離層之概略剖面圖。 Fig. 3 is a schematic cross-sectional view schematically showing an insulating layer with a heat resistant insulating layer according to an embodiment of the present invention.

圖4為示意性表示本發明一實施形態之平板層合型之非雙極型鋰離子蓄電池之外觀立體圖。 Fig. 4 is a perspective view schematically showing the appearance of a flat laminated type non-bipolar lithium ion battery according to an embodiment of the present invention.

圖5為用以說明實施例中捲曲高度之測定方法之示意圖。 Fig. 5 is a schematic view for explaining a method of measuring the curl height in the embodiment.

圖6為表示實施例及比較例所製作之隔離層中參數X之值與捲曲高度之關係的圖表。 Fig. 6 is a graph showing the relationship between the value of the parameter X and the curl height in the separator produced in the examples and the comparative examples.

圖7為表示實施例及比較例所製作之隔離層中參數Y 之值與捲曲高度及電池速率特性之關係的圖表。 Figure 7 is a graph showing the parameters Y in the separation layer produced in the examples and comparative examples. A graph of the relationship between the value and the curl height and battery rate characteristics.

10‧‧‧層合型電池(鋰離子蓄電池) 10‧‧‧Laminated battery (lithium ion battery)

11‧‧‧正極集電體 11‧‧‧ positive current collector

12‧‧‧負極集電體 12‧‧‧Negative current collector

13‧‧‧正極活性物質層 13‧‧‧positive active material layer

15‧‧‧負極活性物質層 15‧‧‧Negative active material layer

17‧‧‧電解質層 17‧‧‧ electrolyte layer

19‧‧‧單電池層 19‧‧‧Single cell layer

21‧‧‧發電要件 21‧‧‧Power generation requirements

25‧‧‧正極集電板 25‧‧‧ positive current collector board

27‧‧‧負極集電板 27‧‧‧Negative current collector board

29‧‧‧電池外裝材(層合膜) 29‧‧‧Battery exterior material (laminated film)

Claims (9)

一種電裝置用之附有耐熱絕緣層之隔離層，其特徵為具有：樹脂多孔質基體，及形成於前述樹脂多孔質基體兩面上且含有熔點或熱軟化點為150℃以上之耐熱粒子之耐熱絕緣層，且以數式1表示之參數X為0.15以上： 式中，A’及A”為形成於前述樹脂多孔質基體兩面上之各耐熱絕緣層之厚度(μm)，此時，A’≧A”，C為前述附有耐熱絕緣層之隔離層之總厚度(μm)。 An insulating layer with a heat-resistant insulating layer for an electric device, comprising: a resin porous substrate; and heat-resistant particles formed on both surfaces of the resin porous substrate and having a melting point or a heat softening point of 150 ° C or more The insulating layer, and the parameter X expressed by the formula 1 is 0.15 or more: In the formula, A' and A" are the thickness (μm) of each of the heat-resistant insulating layers formed on both surfaces of the resin porous substrate, and in this case, A'≧A", C is the above-mentioned separator having a heat-resistant insulating layer. Total thickness (μm). 如申請專利範圍第1項之附有耐熱絕緣層之隔離層，其以數式2表示之參數Y為0.3~0.7之範圍： 式中D為耐熱絕緣層之孔隙率(%)。 For example, in the first application of the patent scope, the insulation layer with a heat-resistant insulating layer is represented by the formula 2, and the parameter Y is in the range of 0.3 to 0.7: Wherein D is the porosity (%) of the heat resistant insulating layer. 如申請專利範圍第1或2項之附有耐熱絕緣層之隔離層，其中前述參數X為0.20以上。 The separator of the heat resistant insulating layer is attached to the first or second aspect of the patent application, wherein the aforementioned parameter X is 0.20 or more. 如申請專利範圍第1至3項中任一項之附有耐熱絕緣層之隔離層，其中前述耐熱粒子為無機氧化物粒子。 The separator having a heat resistant insulating layer, wherein the heat resistant particles are inorganic oxide particles, as claimed in any one of claims 1 to 3. 如申請專利範圍第1至3項中任一項之附有耐熱絕緣層之隔離層，其中前述耐熱粒子為有機樹脂粒子。 A separator having a heat resistant insulating layer, wherein the heat resistant particles are organic resin particles, as claimed in any one of claims 1 to 3. 如申請專利範圍第1至5項中任一項之附有耐熱絕緣層之隔離層，其中前述耐熱絕緣層之孔隙率為40~70%。 The separator having a heat resistant insulating layer as disclosed in any one of claims 1 to 5, wherein the heat resistant insulating layer has a porosity of 40 to 70%. 如申請專利範圍第1至6項中任一項之附有耐熱絕緣層之隔離層，其中前述耐熱絕緣層之厚度總計為5~200μm，前述耐熱絕緣層之厚度的比(A’/A”)為1.0~1.2。 The separator of the heat resistant insulating layer, wherein the thickness of the heat resistant insulating layer is 5 to 200 μm in total, and the ratio of the thickness of the heat resistant insulating layer (A'/ A") is 1.0~1.2. 一種電裝置用之電解質層，其特徵為含有如申請專利範圍第1至7項中任一項之附有耐熱絕緣層之隔離層、與耐熱絕緣層之隔離層之樹脂多孔質基體及於耐熱絕緣層之內部含有之電解質。 An electrolyte layer for an electric device, characterized by comprising a resin porous substrate having a heat-resistant insulating layer-containing separator layer and a heat-resistant insulating layer-separating layer as in any one of claims 1 to 7 and heat-resistant The electrolyte contained inside the insulating layer. 一種電裝置，其特徵為含有如申請專利範圍第1至7項中任一項之附有耐熱絕緣層之隔離層。 An electric device characterized by comprising an insulating layer with a heat resistant insulating layer as claimed in any one of claims 1 to 7.
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